WO2020063160A1 - Wavelength conversion material of high thermal conductivity - Google Patents

Wavelength conversion material of high thermal conductivity Download PDF

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Publication number
WO2020063160A1
WO2020063160A1 PCT/CN2019/100491 CN2019100491W WO2020063160A1 WO 2020063160 A1 WO2020063160 A1 WO 2020063160A1 CN 2019100491 W CN2019100491 W CN 2019100491W WO 2020063160 A1 WO2020063160 A1 WO 2020063160A1
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diamond
wavelength conversion
conversion material
particles
coated
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PCT/CN2019/100491
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French (fr)
Chinese (zh)
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李乾
刘莹莹
王艳刚
许颜正
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深圳光峰科技股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon

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  • the invention relates to a high thermal conductivity wavelength conversion material and a preparation method thereof.
  • fluorescent materials ie, wavelength conversion materials
  • high brightness high thermal conductivity
  • high optical conversion efficiency high optical conversion efficiency
  • the function of the wavelength conversion material is to convert the short-wavelength, high-power laser emitted by the laser into longer-wavelength visible light, which is the core component of the laser light source.
  • the performance of the wavelength conversion material directly determines the main performance of the laser light source.
  • the body of the wavelength conversion material is a phosphor, and different packaging methods of the phosphor determine the final performance of the wavelength conversion device.
  • Packaging methods for phosphors include organic resin packaging, organic silicone packaging, and inorganic glass packaging (whose thermal conductivity generally does not exceed 2W / (m ⁇ k)), and luminescent ceramics.
  • the thermal conductivity of traditional YAG ceramics is also relatively low, generally 10-14W / (m ⁇ k).
  • the wavelength conversion device is made into a round rotatable wheel-color wheel, which is matched with a high-performance motor when used. High-speed rotation. This is because the laser power in the laser light source is very high. In addition to the visible light generated by the laser irradiation on the wavelength conversion material, a large amount of heat is also generated.
  • the present invention aims to provide a high thermal conductivity wavelength conversion material and a preparation method thereof, wherein the wavelength conversion material uses diamond having a high thermal conductivity of 1000-2000 W / (m ⁇ k) and a low thermal expansion coefficient.
  • a light-emitting layer is made with phosphor powder and glass powder, so that the heat generated by the light-emitting layer can be quickly diffused out, and the generated heat can be prevented from deteriorating the characteristics of the phosphor, so that it can be made into a high light efficiency, high thermal conductivity, and blue light transmittance.
  • Adjustable luminescent material which can be applied to high-performance laser light source.
  • a wavelength conversion material includes diamond, phosphor, and a glass phase, and the phosphor accounts for 10% to 99% of the total mass of the wavelength conversion material.
  • the ratio of the diamond to the phosphor is 1: (1-5), preferably 1: 1.
  • At least a part of the diamond is in contact with an adjacent diamond or phosphor to form a heat conduction channel of a space network structure.
  • At least part of the surface of the diamond is covered with a layer of titanium oxide, or at least part of the surface of the diamond is covered with a layer of alumina.
  • a part of the surface of the diamond is coated with a layer of titanium oxide, while another part of the surface of the diamond is coated with a layer of alumina.
  • the thickness of the titanium oxide coating layer and the thickness of the aluminum oxide coating layer are both 2-15 ⁇ m.
  • a mass ratio of the diamond coated with titanium oxide to the diamond coated with alumina is 1: (1-10).
  • the phosphor powder accounts for 10% -99%, preferably 20-80% of the total mass of the wavelength conversion material;
  • the diamond coated titanium oxide accounts for 5-50% of the total mass of the wavelength conversion material %, Preferably 10-40%;
  • the diamond coated with alumina occupies 5-50%, preferably 10-40% of the total mass of the wavelength conversion material;
  • the glass phase occupies the total of the wavelength conversion material 20-80% by mass, preferably 20-60%.
  • the surface of the diamond is coated with a layer of titanium oxide, and the surface of the titanium oxide is further coated with a layer of alumina.
  • the thickness of the coating layer of titanium oxide and aluminum oxide is 2-15 ⁇ m.
  • a method for preparing a wavelength conversion material includes the following steps S1: preparing diamond particles having a particle size of 2-20 ⁇ m and fluorescent particles having a particle size of 10-30 um, preferably 15-20 um.
  • a wavelength conversion material including the following steps: S1: preparing diamond particles having a particle size of 2-20 ⁇ m, the particle size is 10-30 um, preferably 15-20 um Phosphor powder, glass powder particles that can be sintered at 600-800 ° C; S2: The surface of all diamond particles is coated with titanium oxide by the sol-gel method, and then the surface of the diamond particles coated with titanium oxide is coated on the surface Further coating a layer of alumina; S3: the diamond particles, the phosphor particles, and the glass powder particles having a double coating layer of titanium oxide and alumina on the surface prepared in step S2 And the organic carrier is mixed uniformly to make a paste, and the paste is printed on the ceramic substrate; and S4: the ceramic substrate having the paste printed thereon prepared in step S3 is sintered to obtain the wavelength conversion material.
  • the invention provides a wavelength conversion material that can achieve both high heat dissipation and high light efficiency, so that high-power and high-power laser excitation can be realized. Because diamond has a high thermal conductivity (typically 1000-2000W / (m ⁇ k)) and a low thermal expansion coefficient, when diamond, phosphor and glass powder are made into a light-emitting layer, on the one hand, it is colorless and transparent.
  • the diamond particles are in contact with the phosphor particles, and a thermal conduction channel with a spatial network structure can be formed between the diamond-diamond / diamond-phosphor / diamond-phosphor-diamond particles, so that the heat generated by the laser irradiating the phosphor quickly diffuses to the surroundings through the thermal conduction channel , Reduce the thermal saturation effect of the phosphor particles, and prevent the reduction of luminous efficiency.
  • coating the alumina and titanium oxide layers on the surface of diamond particles can generate white light, and at the same time, the thermal conductivity of diamond is also exerted, so that it can be made into a light-emitting material with high light efficiency, high thermal conductivity and adjustable blue light transmittance.
  • the luminescent material can be applied to a high-performance laser light source.
  • FIG. 1 is a schematic cross-sectional view of a glass-encapsulated inorganic light-emitting layer according to Embodiment 1 of the present invention.
  • FIG. 2 is a schematic cross-sectional view of a glass-encapsulated inorganic light-emitting layer according to Embodiment 2 of the present invention.
  • FIG. 3 is a color wheel test result spectrum chart showing the comparison of the light effects of the formulations of Comparative Examples 1 and 2 and a formulation without diamond.
  • FIG. 4 is a schematic cross-sectional view of a glass-encapsulated inorganic light-emitting layer according to Embodiment 3 of the present invention.
  • FIG. 5 is a flowchart of preparing a TiO 2 / Al 2 O 3 double-layered structured diamond according to Example 3 of the present invention.
  • a wavelength conversion material is provided, that is, the glass-encapsulated inorganic light-emitting layer 1001 shown in FIG. 1, and a schematic cross-sectional view thereof is shown in FIG. 1.
  • the glass-encapsulated inorganic light-emitting layer 1001 includes phosphor particles 201, colorless and transparent diamond particles 202, and a glass phase 203 formed of glass powder.
  • the glass-encapsulated inorganic light-emitting layer 1001 can be prepared by the following method: colorless and transparent diamond particles with a particle size of 2-20 ⁇ m and YAG: Ce phosphor particles with a particle size of 10-30 um, preferably 15-20 um, optionally 600- 800 ° C sintered glass powder particles and organic carrier are mixed uniformly, and then the uniformly mixed paste is directly printed on the diffuse reflection material.
  • the thickness of the printed paste is about 50-120um, and the paste is printed on it.
  • the above-mentioned diffuse reflection material is put into a muffle furnace and sintered to obtain the above-mentioned glass-encapsulated inorganic light-emitting layer 1001.
  • the mass percentage of YAG: Ce phosphor particles in the entire glass-encapsulated inorganic light-emitting layer 1001 ranges from 10% to 99%, preferably 30% to 80% to achieve a good light emitting effect; colorless and transparent diamond
  • the ratio to the YAG: Ce phosphor particles is 1: (1-5), preferably 1: 1.
  • the phosphor particles 201 and the colorless and transparent diamond particles 202 are both thermally good conductive phases.
  • Colorless and transparent diamond particles 202 are used as thermally conductive fillers, and their thermal conductivity is 1000-2000 W / (m ⁇ k).
  • the particle sizes of the phosphor particles 201 and the colorless and transparent diamond particles 202 are matched.
  • At least part of the diamond particles are in contact with adjacent diamond or phosphor particles to form a thermal conduction channel 204 of a spatial network structure, for example, a diamond-diamond thermal conduction channel is formed.
  • Diamond-fluorescent powder thermal conduction channel or diamond-fluorescent powder-diamond thermal conduction channel as shown in Figure 1.
  • the heat 205 generated by the laser irradiation of the phosphor is transmitted to the diamond particles 202, and the heat is quickly diffused out through the thermal conduction channel 204, thereby reducing the thermal saturation effect of the phosphor particles 201 and improving the luminous stability of the phosphor.
  • the colorless and transparent diamond particles 202 can withstand high temperatures of 850 to 1000 ° C. in air, and are therefore suitable for use as wavelength conversion materials for high-power excitation light sources.
  • colorless and transparent diamond particles 202 are used as the raw materials of the glass-encapsulated inorganic light-emitting layer 1001.
  • diamond particles with low cost and low transparency can be selected as raw materials.
  • the surface of the particles is coated with a layer of aluminum oxide (Al 2 O 3 ) or titanium oxide (TiO 2 ) to obtain white scattering particles, thereby generating white light. Therefore, this embodiment provides another wavelength conversion material, that is, the glass-encapsulated inorganic light-emitting layer 2001 shown in FIG. 2, and a schematic cross-sectional view thereof is shown in FIG. 2.
  • the glass-encapsulated inorganic light-emitting layer 2001 includes phosphor particles 301, diamond particles 302 coated with titanium oxide on the surface, diamond particles 303 coated with aluminum oxide on the surface, and a glass phase 304 formed of glass powder.
  • the glass-encapsulated inorganic light-emitting layer 2001 in this embodiment can be prepared by a method similar to that in Embodiment 1, except that in this embodiment, first, diamond particles 302 and surface packages coated with titanium oxide need to be prepared. Diamond particles 303 covered with alumina. Diamond particles 302 coated with titanium oxide on the surface and diamond particles 303 coated with aluminum oxide on the surface can be prepared by a sol-gel method, and the specific preparation process is as follows.
  • a titanium oxide sol and an alumina sol were prepared.
  • An Al 2 O 3 sol was prepared by a sol-gel method, in which aluminum isopropoxide (C 9 H 21 AlO 3 ) was used as a precursor raw material, nitric acid (HNO 3 ) was used as a peptizer, and deionized water (H 2 O) was used. As a solvent, it is uniformly mixed according to a certain molar ratio, refluxed at 85 ° C. for 10 hours (hours) under a certain stirring speed, and then left to stand for 24 hours, and filtered to obtain an Al 2 O 3 sol.
  • Diamond particle size is 2-20 ⁇ m, which matches the particle size of phosphor particles.
  • the diamond particles were immersed in acetone for ultrasonic cleaning three times, and then dried to obtain clean diamond micropowder.
  • the cleaned diamond fine powder is contained in a copper mesh and immersed in a TiO 2 sol, and left to stand for 1-10 min (minutes), preferably 1 min, and then the copper mesh is removed from the TiO at a certain speed, preferably 1-3 cm / min. 2 sol was pulled out, and the diamond soaked in TiO 2 sol was placed in an oven at 60-80 ° C., dried for 5-10 minutes, and then cooled to obtain a diamond coated with a TiO 2 gel film surface, wherein the film
  • the layer thickness can be 2-15 ⁇ m.
  • the surface of the diamond is coated with Al 2 O 3 by the same experimental method.
  • the cleaned diamond fine powder is contained in a copper mesh and immersed in an Al 2 O 3 sol, and left to stand for 1-10 minutes, preferably 1 minute, and then a certain amount of Speed, preferably 1-3 cm / min, pull the copper mesh out of the Al 2 O 3 sol, place the diamond coated with Al 2 O 3 in an oven at 60-80 ° C, dry it for 5-10 minutes, and then cool it.
  • a diamond coated with an Al 2 O 3 gel film layer on the surface is obtained, wherein the film layer thickness can be 2-15 ⁇ m.
  • the thickness of the TiO 2 film layer and the Al 2 O 3 film layer can be determined according to the number of coatings and the pulling speed. The more coatings, the larger the thickness, the faster the pulling speed, and the thicker the thickness. small.
  • the coated diamond is heat-treated in a muffle furnace.
  • the temperature is slowly raised to 100 ° C for 30 minutes, and then heated to 600 ° C at a rate of 5 ° C / min for 60 minutes.
  • diamond particles having a surface coated with TiO 2 and a surface coated with Al 2 O 3 were prepared .
  • the two coated diamond particles are mixed uniformly at a mass ratio of 1: (1-10), specifically 1: 1, and then with YAG: Ce phosphor with a particle size of 10-30um, preferably 15-20um.
  • the particles, glass powder particles, and organic carrier are mixed uniformly, and then the uniformly mixed paste is directly printed on the aluminum nitride ceramic substrate.
  • the thickness of the printed paste is about 50-120um. Finally, the above-mentioned paste is printed thereon.
  • the aluminum nitride ceramic substrate is put into a muffle furnace for sintering, the sintering temperature is 700-1000 ° C, and the temperature is maintained for 30 min-1 h, thereby obtaining the above-mentioned glass-encapsulated inorganic light-emitting layer 2001.
  • the mass percentage of YAG: Ce phosphor particles in the entire glass-encapsulated inorganic light-emitting layer 2001 ranges from 10% to 99%, preferably 20% to 80% to achieve a good light emitting effect; the surface is coated with titanium oxide
  • the ratio of diamond to phosphor of alumina is 1: (1-5), preferably 1: 1.
  • titanium oxide sol and diamond have good wettability
  • titanium oxide sol is based on non-polar organic substances
  • diamond It is a regular tetrahedron structure. Its surface has fewer polar bonds and is easily wetted by a non-polar aqueous solution. Therefore, the titanium oxide sol has better wettability on the diamond surface, that is, it is easily covered by the titanium oxide sol. If alumina sol is dropped on the surface of diamond coated with titanium oxide sol, it can be observed that alumina sol can spread well on its surface. This is the solution of the third embodiment.
  • the oxidation resistance of the coated diamond has been greatly improved. During the sintering process, the glass phase and the coated diamond can be well wetted, and the bonding strength is greater after cooling.
  • the sol-gel method is used to coat the surface of the titanium oxide and alumina layers on the surface of the diamond, and then mixed with phosphor, glass powder particles, and organic carrier to form a light-emitting layer.
  • the light-emitting layer is generated. The heat quickly diffuses out; on the other hand, the titanium oxide and aluminum oxide layer structure coated on the diamond surface can be well combined with the phosphor, and can be used as white scattering particles to scatter light or generate white light.
  • the mass components of the glass-encapsulated inorganic light-emitting layer 2001 may be: YAG: Ce phosphor accounts for 10-99% of the total mass; diamond coated titanium oxide accounts for 5-50% of the total mass; Diamond with alumina accounts for 5-50% of the total mass; glass accounts for 20-80% of the total mass.
  • the more preferred solution is: YAG: Ce phosphors account for 20-80% of the total mass; diamond-coated diamonds account for 10-40% of the total mass; alumina-coated diamonds account for 10-40 of the total mass %; Glass accounts for 20-60% of the total mass.
  • Comparative Example 1 YAG: Ce phosphor is 30% of the total mass; diamond coated with titanium oxide is 15% of the total mass; diamond coated with alumina is 15% of the total mass; the rest is glass.
  • Comparative Example 2 YAG: Ce phosphor is 27% of the total mass; diamond-coated diamond is 13.5% of the total mass; alumina-coated diamond is 13.5% of the total mass; the rest is glass.
  • diamond with low transparency is used as the diamond raw material
  • the transparency of the diamond is not strictly required in this embodiment, and of course, colorless and transparent diamond can also be used.
  • the diamond particles coated with titanium oxide and alumina layer structure form a light-emitting layer with phosphor powder and glass powder particles.
  • the role of the coated titanium oxide and alumina is mainly to add white light scattering particles, which can scatter light and form the light.
  • the layer can generate white light under blue laser, and the thermal conductivity of diamond is 1000-2000W / (m ⁇ k), which can be the same as in Example 1, in the diamond-diamond / diamond-fluorescent powder / diamond-fluorescent powder-diamond particles
  • a space network structure can form a heat conduction channel between them, which can quickly diffuse the generated heat, so this layer of structure can both generate white light and quickly diffuse the generated heat.
  • the diamond is entirely coated, and in other embodiments, part of the diamond surface may be covered with a layer of titanium oxide, or part of the diamond surface may be covered with a layer of alumina. As long as a part of the diamond is covered by one of the two, a thermal conductivity effect superior to the prior art can be achieved.
  • the glass-encapsulated inorganic light-emitting layer 3001 shown in FIG. 4 includes phosphor particles 401, diamond particles 402 with a double-layer structure of a titanium oxide layer and an aluminum oxide layer on the surface, and a glass phase 403 formed of glass powder.
  • the glass-encapsulated inorganic light-emitting layer 3001 in this embodiment can be prepared by a method similar to that in Embodiment 2, except that all the diamond particles in this embodiment are covered with a titanium oxide layer and an aluminum oxide layer. Layer structure.
  • the manufacturing process of the glass-encapsulated inorganic light-emitting layer 3001 in this embodiment is as follows.
  • Diamond particle size is 2-20 ⁇ m, which matches the particle size of phosphor particles.
  • the diamond particles were immersed in acetone for ultrasonic cleaning three times, and then dried to obtain clean diamond micropowder.
  • the cleaned diamond fine powder is contained in a copper mesh and soaked in a TiO 2 sol, and left to stand for 1-10 min, preferably 1 min, and then the copper mesh is removed from the TiO 2 sol at a certain speed, preferably 1-3 cm / min. Pull out, place the diamond soaked in TiO 2 sol in an oven at 60-80 ° C, dry it for 5-10 minutes, and cool it to obtain diamond coated with TiO 2 gel film on the surface, where the thickness of the film can be It is 2-15 ⁇ m.
  • the surface-coated TiO 2 gel diamond film immersed in the Al 2 O 3 sol , Rest for 1-10min, preferably 1min, and then pull the copper mesh out of the Al 2 O 3 sol at a certain speed, preferably 1-3 cm / min, and the diamond coated with TiO 2 and Al 2 O 3 It was placed in an oven at 60-80 ° C, dried for 5-10 minutes, and then cooled to obtain diamond coated on the surface with a TiO 2 / Al 2 O 3 gel film layer, wherein the film thickness was 2-15 ⁇ m.
  • the thickness of the TiO 2 film layer and the Al 2 O 3 film layer can be determined according to the number of coatings and the pulling speed. The more coatings, the larger the thickness, the faster the pulling speed, and the thicker the thickness. small.
  • the coated diamond is heat-treated in a muffle furnace.
  • the temperature is slowly raised to 100 ° C for 30 minutes, and then heated to 600 ° C at a rate of 5 ° C / min for 60 minutes.
  • diamond particles with a TiO 2 / Al 2 O 3 double-layer structure on the surface are prepared.
  • the process flow chart is shown in FIG. 5.
  • the diamond coated with the titanium oxide and alumina double-layer structure on the surface and the YAG: Ce phosphor particles, glass powder particles, and organic carrier having a particle size of 10-30um, preferably 15-20um are mixed uniformly, and then the mixture is uniformly mixed.
  • the paste is printed directly on the aluminum nitride ceramic substrate.
  • the thickness of the printed paste is about 50-120um.
  • the above aluminum nitride ceramic substrate printed with the paste is placed in a muffle furnace for sintering and sintering. The temperature is 700-1000 ° C, and the temperature is maintained for 30 min-1 h, so as to obtain the glass-encapsulated inorganic light-emitting layer 3001.
  • the mass percentage of YAG: Ce phosphor particles in the entire glass-encapsulated inorganic light-emitting layer 3001 ranges from 10% to 99%, preferably 30% to 80% to achieve a good light emitting effect; the surface is coated with titanium oxide
  • the ratio of diamond to phosphor of alumina is 1: (1-5), preferably 1: 1.
  • titanium oxide sol and diamond have better wettability.
  • the titanium oxide sol uses a non-polar organic substance as the environment, while diamond has a regular tetrahedron structure, and its surface has polar bonds. Less, easy to be wetted by non-polar aqueous solution, so the titanium oxide sol has better wettability on the diamond surface, that is, it is easy to be wrapped by the titanium oxide sol.
  • Alumina sol can spread well on the surface of diamond coated with titanium oxide sol. Due to the irregular shape of the diamond, many have edges and corners, and the diamond particles are better covered by the film. The oxidation resistance of the coated diamond has been greatly improved. During the sintering process, the glass phase and the coated diamond can be well wetted, and the bonding strength is greater after cooling.
  • the sol-gel method is used to coat the double-layered structure of titanium oxide layer and aluminum oxide layer on the diamond surface, and then mixed with phosphor powder, glass powder particles, and organic carrier to form a light-emitting layer.
  • the heat generated by the light-emitting layer is quickly diffused out; on the other hand, the titanium oxide and aluminum oxide layer structure coated on the surface of the diamond can be well combined with the phosphor, and can be used as white scattering particles to scatter light or generate white light.
  • Diamond particles coated with a two-layer structure of titanium oxide layer and aluminum oxide layer form a light-emitting layer with phosphor powder and glass powder particles, and the coated titanium oxide and aluminum oxide
  • the function is mainly to add white light scattering particles, which can scatter light.
  • the formed luminescent layer can generate white light under blue laser light, and the thermal conductivity of diamond is 1000-2000W / (m ⁇ k), which can be used with Example 1 and implementation.
  • a thermal conduction channel with a spatial network structure can be formed between diamond-diamond / diamond-phosphor / diamond-phosphor-diamond particles, and the generated heat can be quickly diffused out, so this layer of structure can produce both white light and The heat generated can be quickly dissipated.
  • the light effect in this embodiment is not much different from the light effect in Embodiment 2, and is improved over the original light effect.

Abstract

A wavelength conversion material, comprising diamond, phosphor, and glass phase. The phosphor is 10-99% of the total mass of the wavelength conversion material, and the ratio of the diamond to the phosphor is 1:(1-5), preferably 1:1. The wavelength conversion material uses diamond having higher thermal conductivity of 1000-2000 W/(m•k) and a lower thermal expansion coefficient as raw material, and heat produced by the wavelength conversion material can be rapidly diffused, so as to prevent the produced heat from degrading the phosphor properties, thereby preparing a luminescent materials of high luminous efficiency, high thermal conductivity, and adjustable blue light transmittance.

Description

一种高导热率波长转换材料High thermal conductivity wavelength conversion material 技术领域Technical field
本发明涉及一种高导热率波长转换材料及其制备方法。The invention relates to a high thermal conductivity wavelength conversion material and a preparation method thereof.
背景技术Background technique
随着激光显示技术的不断发展，蓝色激光激发荧光材料获得可见光的技术获得很大进展。目前，针对激光激发荧光粉的特性开发的荧光材料(即，波长转换材料)要求具有高亮度、高导热性能、光学转换效率高等优良性能。With the continuous development of laser display technology, the technology of blue laser excited fluorescent materials to obtain visible light has made great progress. Currently, fluorescent materials (ie, wavelength conversion materials) developed for the characteristics of laser-excited phosphors are required to have excellent properties such as high brightness, high thermal conductivity, and high optical conversion efficiency.
波长转换材料的作用是将激光器发出的短波长、大功率激光转化成更长波长的可见光，其是激光光源的核心部件。波长转换材料的性能直接决定了激光光源的主要性能。波长转换材料的主体为荧光粉，荧光粉的不同封装方式决定了波长转换装置的最终性能。荧光粉的封装方式包括有机树脂封装、有机硅胶封装和无机玻璃封装(其导热率一般不超过2W/(m·k))，以及发光陶瓷。传统的YAG陶瓷的导热率也相对较低，一般为10-14W/(m·k)，一般将波长转换装置制成圆形可旋转的轮子-色轮，匹配高性能马达后，在使用时高速旋转。这是由于激光光源中的激光功率很高，激光照射在波长转换材料上除了产生可见光之外，同时还会产生大量的热量。The function of the wavelength conversion material is to convert the short-wavelength, high-power laser emitted by the laser into longer-wavelength visible light, which is the core component of the laser light source. The performance of the wavelength conversion material directly determines the main performance of the laser light source. The body of the wavelength conversion material is a phosphor, and different packaging methods of the phosphor determine the final performance of the wavelength conversion device. Packaging methods for phosphors include organic resin packaging, organic silicone packaging, and inorganic glass packaging (whose thermal conductivity generally does not exceed 2W / (m · k)), and luminescent ceramics. The thermal conductivity of traditional YAG ceramics is also relatively low, generally 10-14W / (m · k). Generally, the wavelength conversion device is made into a round rotatable wheel-color wheel, which is matched with a high-performance motor when used. High-speed rotation. This is because the laser power in the laser light source is very high. In addition to the visible light generated by the laser irradiation on the wavelength conversion material, a large amount of heat is also generated.
色轮散热主要有两种形式：一种是通过在马达的高速旋转下，荧光粉层表面直接与环境形成对流散热；另一种是热量先经反射层传导到基板，再由基板表面与环境形成对流散热；但其中发光层面与空气对流散热起主导作用，所以只有提高这个界面的散热效率，才能有效地提升色轮模块的整体散热效率。然而，这些封装材料都具有较低的热导系数，使得大功率激光照射时产生的热量不易扩散出去，从而导致温度上升，影响荧光粉光效，即，使得荧光粉光效下降或失效。There are two main types of heat dissipation of the color wheel: one is through the high-speed rotation of the motor, the surface of the phosphor layer directly forms convection to the heat; Convection heat dissipation is formed; however, the light emitting layer and air convection heat play a leading role, so only by improving the heat dissipation efficiency of this interface can the overall heat dissipation efficiency of the color wheel module be effectively improved. However, these packaging materials all have a low thermal conductivity coefficient, which makes it difficult for the heat generated during the irradiation of high-power lasers to diffuse out, which leads to an increase in temperature and affects the light efficiency of the phosphor, that is, the light efficiency of the phosphor decreases or fails.
因此，有待于提供一种高导热率波长转换材料，其可将发光层产生的热量迅速扩散出去，防止产生的热导致荧光粉特性劣化，从而可制成高光效、高导热率、蓝光透过率可调的发光材料。Therefore, there is a need to provide a wavelength conversion material with high thermal conductivity, which can quickly dissipate the heat generated by the light emitting layer and prevent the generated heat from deteriorating the characteristics of the phosphor, so that it can be made into a high light efficiency, high thermal conductivity, and blue light transmission. Rate-adjustable luminescent material.
发明内容Summary of the Invention
有鉴于此，本发明旨在提供一种高导热率波长转换材料及其制备方法，其中该波长转换材料采用具有较高导热率1000-2000W/(m·k)和较低的热膨胀系数的金刚石作为原料，与荧光粉和玻璃粉制成发光层，使得发光层产生的热量可以迅速扩散出去，防止产生的热导致荧光粉特性劣化，从而可制成高光效、高导热率、蓝光透过率可调的发光材料，该发光材料可应用于高性能激光光源。In view of this, the present invention aims to provide a high thermal conductivity wavelength conversion material and a preparation method thereof, wherein the wavelength conversion material uses diamond having a high thermal conductivity of 1000-2000 W / (m · k) and a low thermal expansion coefficient. As a raw material, a light-emitting layer is made with phosphor powder and glass powder, so that the heat generated by the light-emitting layer can be quickly diffused out, and the generated heat can be prevented from deteriorating the characteristics of the phosphor, so that it can be made into a high light efficiency, high thermal conductivity, and blue light transmittance. Adjustable luminescent material, which can be applied to high-performance laser light source.
根据本发明的第一方面，提供了一种波长转换材料，其中，所述波长转换材料包含金刚石、荧光粉和玻璃相，所述荧光粉占所述波长转换材料总质量的10％-99％，所述金刚石与所述荧光粉的比例为1:(1-5)，优选1:1。According to a first aspect of the present invention, a wavelength conversion material is provided, wherein the wavelength conversion material includes diamond, phosphor, and a glass phase, and the phosphor accounts for 10% to 99% of the total mass of the wavelength conversion material. The ratio of the diamond to the phosphor is 1: (1-5), preferably 1: 1.
进一步地，至少部分所述金刚石与相邻的金刚石或者荧光粉之间接触从而形成空间网络结构的导热通道。Further, at least a part of the diamond is in contact with an adjacent diamond or phosphor to form a heat conduction channel of a space network structure.
进一步地，至少部分所述金刚石表面包覆有一层氧化钛，或者至少部分所述金刚石表面包覆有一层氧化铝。Further, at least part of the surface of the diamond is covered with a layer of titanium oxide, or at least part of the surface of the diamond is covered with a layer of alumina.
进一步地，一部分所述金刚石表面包覆有一层氧化钛，同时另一部分所述金刚石表面包覆有一层氧化铝。Further, a part of the surface of the diamond is coated with a layer of titanium oxide, while another part of the surface of the diamond is coated with a layer of alumina.
进一步地，所述氧化钛包覆层的厚度和所述氧化铝包覆层的厚度均为2-15μm。Further, the thickness of the titanium oxide coating layer and the thickness of the aluminum oxide coating layer are both 2-15 μm.
进一步地，包覆有氧化钛的所述金刚石与包覆有氧化铝的所述金刚石的质量比为1:(1-10)。Further, a mass ratio of the diamond coated with titanium oxide to the diamond coated with alumina is 1: (1-10).
进一步地，所述荧光粉占所述波长转换材料总质量的10％-99％，优选为20-80％；包覆有氧化钛的所述金刚石占所述波长转换材料总质量的5-50％，优选为10-40％；包覆有氧化铝的所述金刚石占所述波长转换材 料总质量的5-50％，优选为10-40％；所述玻璃相占所述波长转换材料总质量的20-80％，优选为20-60％。Further, the phosphor powder accounts for 10% -99%, preferably 20-80% of the total mass of the wavelength conversion material; the diamond coated titanium oxide accounts for 5-50% of the total mass of the wavelength conversion material %, Preferably 10-40%; the diamond coated with alumina occupies 5-50%, preferably 10-40% of the total mass of the wavelength conversion material; the glass phase occupies the total of the wavelength conversion material 20-80% by mass, preferably 20-60%.
进一步地，所述金刚石的表面包覆有一层氧化钛，并且在氧化钛的表面还包覆有一层氧化铝。Further, the surface of the diamond is coated with a layer of titanium oxide, and the surface of the titanium oxide is further coated with a layer of alumina.
进一步地，所述氧化钛和氧化铝的包覆层的厚度为2-15μm。Further, the thickness of the coating layer of titanium oxide and aluminum oxide is 2-15 μm.
根据本发明的第二方面，提供了一种波长转换材料的制备方法，所述方法包括以下步骤S1：准备粒度为2-20μm的金刚石颗粒以及粒度为10-30um、优选为15-20um的荧光粉颗粒、能够在600-800℃烧结的玻璃粉颗粒；S2：采用溶胶凝胶法在一部分所述金刚石颗粒的表面包覆一层氧化钛，并在另一部分所述金刚石颗粒的表面包覆一层氧化铝；S3：将步骤S2中制备得到的表面具有包覆层的所述金刚石颗粒、所述荧光粉颗粒、所述玻璃粉颗粒以及有机载体混合均匀以制成浆料，并将该浆料印刷在陶瓷基板上；和S4：将步骤S3中制备得到的其上印刷有浆料的陶瓷基板进行烧结，制得所述波长转换材料。According to a second aspect of the present invention, a method for preparing a wavelength conversion material is provided. The method includes the following steps S1: preparing diamond particles having a particle size of 2-20 μm and fluorescent particles having a particle size of 10-30 um, preferably 15-20 um. Powder particles, glass powder particles that can be sintered at 600-800 ° C; S2: using a sol-gel method to coat a part of the surface of the diamond particles with a layer of titanium oxide, and coating the surface of another part of the diamond particles with a Layer alumina; S3: the diamond particles, the phosphor particles, the glass frit particles and the organic carrier having the coating layer on the surface prepared in step S2 are mixed uniformly to make a slurry, and the slurry is prepared; The material is printed on a ceramic substrate; and S4: the ceramic substrate having the paste printed thereon prepared in step S3 is sintered to obtain the wavelength conversion material.
根据本发明的第三方面，提供了另一种波长转换材料的制备方法，所述方法包括以下步骤：S1：准备粒度为2-20μm的金刚石颗粒、粒度为10-30um，优选为15-20um的荧光粉颗粒、能够在600-800℃烧结的玻璃粉颗粒；S2：采用溶胶凝胶法在所有金刚石颗粒的表面包覆一层氧化钛，然后在包覆有氧化钛的金刚石颗粒的表面上再包覆一层氧化铝；S3：将步骤S2中制备得到的表面具有一层氧化钛和一层氧化铝的双包覆层的所述金刚石颗粒、所述荧光粉颗粒、所述玻璃粉颗粒以及有机载体混合均匀以制成浆料，并将该浆料印刷在陶瓷基板上；和S4：将步骤S3中制备得到的其上印刷有浆料的陶瓷基板进行烧结，制得所述波长转换材料。According to a third aspect of the present invention, there is provided another method for preparing a wavelength conversion material, the method including the following steps: S1: preparing diamond particles having a particle size of 2-20 μm, the particle size is 10-30 um, preferably 15-20 um Phosphor powder, glass powder particles that can be sintered at 600-800 ° C; S2: The surface of all diamond particles is coated with titanium oxide by the sol-gel method, and then the surface of the diamond particles coated with titanium oxide is coated on the surface Further coating a layer of alumina; S3: the diamond particles, the phosphor particles, and the glass powder particles having a double coating layer of titanium oxide and alumina on the surface prepared in step S2 And the organic carrier is mixed uniformly to make a paste, and the paste is printed on the ceramic substrate; and S4: the ceramic substrate having the paste printed thereon prepared in step S3 is sintered to obtain the wavelength conversion material.
有益效果Beneficial effect
本发明提供了一种既能实现高散热又能实现高光效的波长转换材料，从而可实现高功率及较高功率的激光激发。由于金刚石有较高导热率(一般为1000-2000W/(m·k))和较低的热膨胀系数，所以当将金刚石、荧光粉和玻璃粉制成发光层时，一方面，无色透明的金刚石颗粒与荧光 粉颗粒接触，金刚石-金刚石/金刚石-荧光粉/金刚石-荧光粉-金刚石颗粒之间可以形成空间网络结构的导热通道，使得激光照射荧光粉产生的热量迅速通过导热通道向周围扩散，降低荧光粉颗粒的热饱和效应，防止发光效率降低。另一方面，在金刚石颗粒表面包覆氧化铝和氧化钛层可产生白光，同时金刚石的导热性能也得到发挥，从而可制成高光效、高导热率、蓝光透过率可调的发光材料，该发光材料可应用于高性能激光光源。The invention provides a wavelength conversion material that can achieve both high heat dissipation and high light efficiency, so that high-power and high-power laser excitation can be realized. Because diamond has a high thermal conductivity (typically 1000-2000W / (m · k)) and a low thermal expansion coefficient, when diamond, phosphor and glass powder are made into a light-emitting layer, on the one hand, it is colorless and transparent. The diamond particles are in contact with the phosphor particles, and a thermal conduction channel with a spatial network structure can be formed between the diamond-diamond / diamond-phosphor / diamond-phosphor-diamond particles, so that the heat generated by the laser irradiating the phosphor quickly diffuses to the surroundings through the thermal conduction channel , Reduce the thermal saturation effect of the phosphor particles, and prevent the reduction of luminous efficiency. On the other hand, coating the alumina and titanium oxide layers on the surface of diamond particles can generate white light, and at the same time, the thermal conductivity of diamond is also exerted, so that it can be made into a light-emitting material with high light efficiency, high thermal conductivity and adjustable blue light transmittance. The luminescent material can be applied to a high-performance laser light source.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
附图表示本文所述的非限制性示例性实施例。本领域技术人员将要理解的是，附图不一定按比例绘制，而是用于重点说明本发明的原理。在附图中：The drawings represent non-limiting exemplary embodiments described herein. Those skilled in the art will understand that the drawings are not necessarily drawn to scale, but are used to highlight the principles of the invention. In the drawings:
图1是根据本发明实施例1的玻璃封装无机发光层的截面示意图。FIG. 1 is a schematic cross-sectional view of a glass-encapsulated inorganic light-emitting layer according to Embodiment 1 of the present invention.
图2是根据本发明实施例2的玻璃封装无机发光层的截面示意图。FIG. 2 is a schematic cross-sectional view of a glass-encapsulated inorganic light-emitting layer according to Embodiment 2 of the present invention.
图3是示出了对比例1和2的配方与不含金刚石的配方的光效比较结果的色轮测试结果光谱图。FIG. 3 is a color wheel test result spectrum chart showing the comparison of the light effects of the formulations of Comparative Examples 1 and 2 and a formulation without diamond.
图4是根据本发明实施例3的玻璃封装无机发光层的截面示意图。4 is a schematic cross-sectional view of a glass-encapsulated inorganic light-emitting layer according to Embodiment 3 of the present invention.
图5是根据本发明实施例3的制备包覆TiO 2/Al 2O 3双膜层结构的金刚石的流程图。 FIG. 5 is a flowchart of preparing a TiO 2 / Al 2 O 3 double-layered structured diamond according to Example 3 of the present invention.
附图标记列表：List of reference signs:
1001：玻璃封装无机发光层1001: Glass-encapsulated inorganic light-emitting layer
201：荧光粉颗粒201: Phosphor particles
202：无色透明的金刚石颗粒202: colorless and transparent diamond particles
203：玻璃粉形成的玻璃相203: glass phase formed by glass powder
204：金刚石-金刚石/金刚石-荧光粉/金刚石-荧光粉-金刚石之间形成的导热通道204: Thermal conduction channel formed between diamond-diamond / diamond-phosphor / diamond-phosphor-diamond
205：激光照射荧光粉产生的热205: Heat generated by laser irradiating phosphor
2001：玻璃封装无机发光层2001: Glass-encapsulated inorganic light-emitting layer
301：荧光粉颗粒301: phosphor particles
302：表面包覆有氧化钛的金刚石颗粒302: Diamond particles coated with titanium oxide on the surface
303：表面包覆有氧化铝的金刚石颗粒303: Diamond particles coated with alumina on the surface
304：玻璃粉形成的玻璃相304: glass phase formed by glass powder
3001：玻璃封装无机发光层3001: Glass-encapsulated inorganic light-emitting layer
401：荧光粉颗粒401: phosphor particles
402：表面包覆有氧化钛和氧化铝双膜层结构的金刚石颗粒402: Diamond particles with double-layered structure of titanium oxide and aluminum oxide on the surface
403：玻璃粉形成的玻璃相403: glass phase formed by glass powder
具体实施方式detailed description
以下，参照附图更全面地说明本发明的一个或多个示例性实施例，在附图中，本领域技术人员能够容易地确定本发明的一个或多个示例性实施例。如本领域技术人员应认识到的，只要不脱离本发明的精神或范围，可以以各种不同的方式对所述示例性实施例进行修改，本发明的精神或范围不限于本文所述的示例性实施例。Hereinafter, one or more exemplary embodiments of the present invention will be described more fully with reference to the accompanying drawings, in which those skilled in the art can easily determine one or more exemplary embodiments of the present invention. As those skilled in the art should realize, the described exemplary embodiments may be modified in various different ways without departing from the spirit or scope of the invention, and the spirit or scope of the invention is not limited to the examples described herein. Sexual embodiment.
现在参照附图对本发明的实施例进行详细说明。Embodiments of the present invention will now be described in detail with reference to the drawings.
实施例1Example 1
在本实施例中，提供了一种波长转换材料，即如图1所示的玻璃封装无机发光层1001，其截面示意图如图1所示。从图1可以看出，玻璃封装无机发光层1001包括荧光粉颗201、无色透明的金刚石颗粒202和玻璃粉形成的玻璃相203。In this embodiment, a wavelength conversion material is provided, that is, the glass-encapsulated inorganic light-emitting layer 1001 shown in FIG. 1, and a schematic cross-sectional view thereof is shown in FIG. 1. As can be seen from FIG. 1, the glass-encapsulated inorganic light-emitting layer 1001 includes phosphor particles 201, colorless and transparent diamond particles 202, and a glass phase 203 formed of glass powder.
上述玻璃封装无机发光层1001可以通过如下方法制备：将粒度为2-20μm的无色透明的金刚石颗粒与粒度为10-30um，优选为15-20um的YAG:Ce荧光粉颗粒、可选600-800℃烧结的种类的玻璃粉颗粒、有机载体混合均匀，然后将混合均匀的浆料直接印刷在漫反射材料上，印刷的浆料的厚度为约50-120um，最后将其上印刷有浆料的上述漫反射材 料放入马弗炉中进行烧结，从而获得上述玻璃封装无机发光层1001。需要指出的是，YAG:Ce荧光粉颗粒占整个玻璃封装无机发光层1001的质量百分比的范围为10％-99％，优选为30％-80％以达到良好的发光效果；无色透明的金刚石与YAG:Ce荧光粉颗粒的比例为1:(1-5)，优选为1:1。激光照射玻璃封装无机发光层1001时可出射黄光或者绿光。由于无色透明的金刚石颗粒202的光透过率较高，所以提高了光效。The glass-encapsulated inorganic light-emitting layer 1001 can be prepared by the following method: colorless and transparent diamond particles with a particle size of 2-20 μm and YAG: Ce phosphor particles with a particle size of 10-30 um, preferably 15-20 um, optionally 600- 800 ° C sintered glass powder particles and organic carrier are mixed uniformly, and then the uniformly mixed paste is directly printed on the diffuse reflection material. The thickness of the printed paste is about 50-120um, and the paste is printed on it. The above-mentioned diffuse reflection material is put into a muffle furnace and sintered to obtain the above-mentioned glass-encapsulated inorganic light-emitting layer 1001. It should be noted that the mass percentage of YAG: Ce phosphor particles in the entire glass-encapsulated inorganic light-emitting layer 1001 ranges from 10% to 99%, preferably 30% to 80% to achieve a good light emitting effect; colorless and transparent diamond The ratio to the YAG: Ce phosphor particles is 1: (1-5), preferably 1: 1. When the laser light irradiates the glass-encapsulated inorganic light emitting layer 1001, yellow light or green light can be emitted. Since the light transmittance of the colorless and transparent diamond particles 202 is high, the light efficiency is improved.
在本实施例中，荧光粉颗201和无色透明的金刚石颗粒202均是热的良好的传导相。无色透明的金刚石颗粒202作为导热填充材料，其导热系数为1000-2000W/(m·k)。荧光粉颗201和无色透明的金刚石颗粒202的粒度相匹配，至少部分金刚石颗粒与相邻的金刚石或者荧光粉颗粒之间接触从而形成空间网络结构的导热通道204，例如形成金刚石-金刚石导热通道、金刚石-荧光粉导热通道或者金刚石-荧光粉-金刚石导热通道，如图1所示。激光照射荧光粉产生的热205传导到金刚石颗粒202上，这些热量通过导热通道204快速扩散出去，从而降低了荧光粉颗粒201的热饱和效应，提高了荧光粉的发光稳定性。此外，无色透明的金刚石颗粒202可以在空气中耐850～1000℃的高温，因此适于用作高功率激发光源的波长转换材料。In this embodiment, the phosphor particles 201 and the colorless and transparent diamond particles 202 are both thermally good conductive phases. Colorless and transparent diamond particles 202 are used as thermally conductive fillers, and their thermal conductivity is 1000-2000 W / (m · k). The particle sizes of the phosphor particles 201 and the colorless and transparent diamond particles 202 are matched. At least part of the diamond particles are in contact with adjacent diamond or phosphor particles to form a thermal conduction channel 204 of a spatial network structure, for example, a diamond-diamond thermal conduction channel is formed. , Diamond-fluorescent powder thermal conduction channel or diamond-fluorescent powder-diamond thermal conduction channel, as shown in Figure 1. The heat 205 generated by the laser irradiation of the phosphor is transmitted to the diamond particles 202, and the heat is quickly diffused out through the thermal conduction channel 204, thereby reducing the thermal saturation effect of the phosphor particles 201 and improving the luminous stability of the phosphor. In addition, the colorless and transparent diamond particles 202 can withstand high temperatures of 850 to 1000 ° C. in air, and are therefore suitable for use as wavelength conversion materials for high-power excitation light sources.
实施例2Example 2
在上述实施例1中使用无色透明的金刚石颗粒202作为玻璃封装无机发光层1001的原料。然而，由于无色透明的金刚石颗粒价格较高，因此作为进一步的优化，在本实施例中，可以选用成本较低的透明度低的金刚石颗粒作为原料，通过采用溶胶凝胶方式在透明度低的金刚石颗粒表面包覆一层氧化铝(Al 2O 3)或氧化钛(TiO 2)而获得白色散射粒子，从而可以产生白光。因此，本实施例提供了另一种波长转换材料，即如图2所示的玻璃封装无机发光层2001，其截面示意图如图2所示。从图2可以看出，玻璃封装无机发光层2001包括荧光粉颗粒301、表面包覆有氧化钛的金刚石颗粒302、表面包覆有氧化铝的金刚石颗粒303和玻璃粉形成的玻璃相304。 In the above-mentioned Embodiment 1, colorless and transparent diamond particles 202 are used as the raw materials of the glass-encapsulated inorganic light-emitting layer 1001. However, since the price of colorless and transparent diamond particles is high, as a further optimization, in this embodiment, diamond particles with low cost and low transparency can be selected as raw materials. The surface of the particles is coated with a layer of aluminum oxide (Al 2 O 3 ) or titanium oxide (TiO 2 ) to obtain white scattering particles, thereby generating white light. Therefore, this embodiment provides another wavelength conversion material, that is, the glass-encapsulated inorganic light-emitting layer 2001 shown in FIG. 2, and a schematic cross-sectional view thereof is shown in FIG. 2. As can be seen from FIG. 2, the glass-encapsulated inorganic light-emitting layer 2001 includes phosphor particles 301, diamond particles 302 coated with titanium oxide on the surface, diamond particles 303 coated with aluminum oxide on the surface, and a glass phase 304 formed of glass powder.
本实施例中的玻璃封装无机发光层2001可以以与实施例1类似的方法来制备，其中不同之处在于，在本实施例中需要首先制备表面包覆有 氧化钛的金刚石颗粒302和表面包覆有氧化铝的金刚石颗粒303。表面包覆有氧化钛的金刚石颗粒302和表面包覆有氧化铝的金刚石颗粒303可以通过溶胶凝胶法来制备，具体制备过程如下所述。The glass-encapsulated inorganic light-emitting layer 2001 in this embodiment can be prepared by a method similar to that in Embodiment 1, except that in this embodiment, first, diamond particles 302 and surface packages coated with titanium oxide need to be prepared. Diamond particles 303 covered with alumina. Diamond particles 302 coated with titanium oxide on the surface and diamond particles 303 coated with aluminum oxide on the surface can be prepared by a sol-gel method, and the specific preparation process is as follows.
首先，制备氧化钛溶胶和氧化铝溶胶。First, a titanium oxide sol and an alumina sol were prepared.
氧化钛溶胶的制备：Preparation of titanium oxide sol:
采用分析纯的三乙醇胺(N(OC 2H 5) 3)、无水乙醇(C 2H 5OH)、钛酸丁酯(Ti(OC 4H 9) 4)和去离子水(H 2O)作为原料，将其按一定的摩尔比配制成混合溶液，在磁力搅拌器的高速搅拌下制成透明TiO 2溶胶。TiO 2溶胶转变成三维网络状醇凝胶-(TiO 2)n-，其结构如下所示。 Analytical pure triethanolamine (N (OC 2 H 5 ) 3 ), anhydrous ethanol (C 2 H 5 OH), butyl titanate (Ti (OC 4 H 9 ) 4 ), and deionized water (H 2 O ) As a raw material, prepare a mixed solution at a certain molar ratio, and make a transparent TiO 2 sol under high-speed stirring of a magnetic stirrer. The TiO 2 sol is transformed into a three-dimensional network-like alcohol gel- (TiO 2 ) n-, and its structure is shown below.
Figure PCTCN2019100491-appb-000001
Figure PCTCN2019100491-appb-000001
氧化铝溶胶的制备：Preparation of alumina sol:
采用溶胶凝胶法制备Al 2O 3溶胶，其中以异丙醇铝(C 9H 21AlO 3)为前驱体原料，以硝酸(HNO 3)为胶溶剂，以去离子水(H 2O)为溶剂，将其按一定的摩尔比均匀混合，在一定的搅拌速度下在85℃下回流10h(小时)，然后静置24h，过滤可得到Al 2O 3溶胶。 An Al 2 O 3 sol was prepared by a sol-gel method, in which aluminum isopropoxide (C 9 H 21 AlO 3 ) was used as a precursor raw material, nitric acid (HNO 3 ) was used as a peptizer, and deionized water (H 2 O) was used. As a solvent, it is uniformly mixed according to a certain molar ratio, refluxed at 85 ° C. for 10 hours (hours) under a certain stirring speed, and then left to stand for 24 hours, and filtered to obtain an Al 2 O 3 sol.
然后，对金刚石进行清洗。金刚石粒度为2-20μm，与荧光粉颗粒粒度相匹配。将金刚石颗粒用丙酮浸泡超声清洗三次，然后干燥得到洁净的金刚石微粉。Then, the diamond is washed. Diamond particle size is 2-20 μm, which matches the particle size of phosphor particles. The diamond particles were immersed in acetone for ultrasonic cleaning three times, and then dried to obtain clean diamond micropowder.
接着，将清洗干净的金刚石微粉用铜网盛装并浸泡在TiO 2溶胶中，静置1-10min(分钟)，优选1min，然后以一定的速度，优选1-3cm/min，将铜网从TiO 2溶胶中提拉出来，将在TiO 2溶胶中浸泡过的金刚石放置于60-80℃的烘箱中，干燥5-10min后冷却，得到表面涂覆有TiO 2凝胶膜层的金刚石，其中膜层厚度可以为2-15μm。 Next, the cleaned diamond fine powder is contained in a copper mesh and immersed in a TiO 2 sol, and left to stand for 1-10 min (minutes), preferably 1 min, and then the copper mesh is removed from the TiO at a certain speed, preferably 1-3 cm / min. 2 sol was pulled out, and the diamond soaked in TiO 2 sol was placed in an oven at 60-80 ° C., dried for 5-10 minutes, and then cooled to obtain a diamond coated with a TiO 2 gel film surface, wherein the film The layer thickness can be 2-15 μm.
接着，采用相同的实验方法在金刚石表面涂覆Al 2O 3，将清洗干净的金刚石微粉用铜网盛装并浸泡在Al 2O 3溶胶中，静置1-10min，优选1min，然后以一定的速度，优选1-3cm/min，将铜网从Al 2O 3溶胶中提拉 出来，将涂覆有Al 2O 3的金刚石放置于60-80℃的烘箱中，干燥5-10min后冷却，得到表面涂覆有Al 2O 3凝胶膜层的金刚石，其中膜层厚度可以为2-15μm。 Next, the surface of the diamond is coated with Al 2 O 3 by the same experimental method. The cleaned diamond fine powder is contained in a copper mesh and immersed in an Al 2 O 3 sol, and left to stand for 1-10 minutes, preferably 1 minute, and then a certain amount of Speed, preferably 1-3 cm / min, pull the copper mesh out of the Al 2 O 3 sol, place the diamond coated with Al 2 O 3 in an oven at 60-80 ° C, dry it for 5-10 minutes, and then cool it. A diamond coated with an Al 2 O 3 gel film layer on the surface is obtained, wherein the film layer thickness can be 2-15 μm.
需要指出的是，TiO 2膜层和Al 2O 3膜层的厚度可根据涂覆的次数和提拉的速度决定，涂覆次数越多，厚度越大，提拉的速度越快，厚度越小。 It should be noted that the thickness of the TiO 2 film layer and the Al 2 O 3 film layer can be determined according to the number of coatings and the pulling speed. The more coatings, the larger the thickness, the faster the pulling speed, and the thicker the thickness. small.
接着，涂膜完成后，用马弗炉对涂膜后的金刚石进行热处理，刚开始缓慢升温至100℃，保温30min，然后以5℃/min的速度升温至600℃，保温60min，然后随炉冷却至室温，即制得表面涂覆有TiO 2和表面涂覆有Al 2O 3层结构的金刚石颗粒。 Next, after the coating is completed, the coated diamond is heat-treated in a muffle furnace. The temperature is slowly raised to 100 ° C for 30 minutes, and then heated to 600 ° C at a rate of 5 ° C / min for 60 minutes. After cooling to room temperature, diamond particles having a surface coated with TiO 2 and a surface coated with Al 2 O 3 were prepared .
然后，将两种包覆处理的金刚石颗粒按质量比1:(1-10)，具体地为1:1混合均匀，再与粒度为10-30um，优选为15-20um的YAG:Ce荧光粉颗粒、玻璃粉颗粒、有机载体混合均匀，然后将混合均匀的浆料直接印刷在氮化铝陶瓷基板上，印刷的浆料的厚度为约50-120um，最后将其上印刷有浆料的上述氮化铝陶瓷基板放入马弗炉中进行烧结，烧结温度为700-1000℃，保温30min-1h，从而获得上述玻璃封装无机发光层2001。需要指出的是，YAG:Ce荧光粉颗粒占整个玻璃封装无机发光层2001的质量百分比范围为10％-99％，优选为20％-80％以达到良好的发光效果；表面包覆有氧化钛和氧化铝的金刚石与荧光粉的比例为1:(1-5)，优选1:1。Then, the two coated diamond particles are mixed uniformly at a mass ratio of 1: (1-10), specifically 1: 1, and then with YAG: Ce phosphor with a particle size of 10-30um, preferably 15-20um. The particles, glass powder particles, and organic carrier are mixed uniformly, and then the uniformly mixed paste is directly printed on the aluminum nitride ceramic substrate. The thickness of the printed paste is about 50-120um. Finally, the above-mentioned paste is printed thereon. The aluminum nitride ceramic substrate is put into a muffle furnace for sintering, the sintering temperature is 700-1000 ° C, and the temperature is maintained for 30 min-1 h, thereby obtaining the above-mentioned glass-encapsulated inorganic light-emitting layer 2001. It should be noted that the mass percentage of YAG: Ce phosphor particles in the entire glass-encapsulated inorganic light-emitting layer 2001 ranges from 10% to 99%, preferably 20% to 80% to achieve a good light emitting effect; the surface is coated with titanium oxide The ratio of diamond to phosphor of alumina is 1: (1-5), preferably 1: 1.
将金刚石表面包覆氧化钛或者氧化铝后，其优越性表现在以下几个方面：氧化钛溶胶和金刚石的润湿性较好，氧化钛溶胶是以非极性有机类物质为环境，而金刚石是正四面体结构，其表面极性键较少，容易被非极性类水溶液润湿，所以氧化钛溶胶在金刚石表面的润湿性较好，即易被氧化钛溶胶包裹。若在被氧化钛溶胶包覆的金刚石表面上滴入氧化铝溶胶，可以观察到氧化铝溶胶能在其表面上很好的铺展。这是实施例三的方案。After the surface of diamond is coated with titanium oxide or aluminum oxide, its advantages are shown in the following aspects: titanium oxide sol and diamond have good wettability, titanium oxide sol is based on non-polar organic substances, and diamond It is a regular tetrahedron structure. Its surface has fewer polar bonds and is easily wetted by a non-polar aqueous solution. Therefore, the titanium oxide sol has better wettability on the diamond surface, that is, it is easily covered by the titanium oxide sol. If alumina sol is dropped on the surface of diamond coated with titanium oxide sol, it can be observed that alumina sol can spread well on its surface. This is the solution of the third embodiment.
由于金刚石形状不规则，很多有棱角，金刚石颗粒棱角处也被膜层包覆的较好。被包覆后的金刚石抗氧化性能得到大幅度提高。烧结过程中的玻璃相和被包覆的金刚石能够很好的润湿，冷却后结合强度较大。Due to the irregular shape of the diamond, many have edges and corners, and the diamond particles are better covered by the film. The oxidation resistance of the coated diamond has been greatly improved. During the sintering process, the glass phase and the coated diamond can be well wetted, and the bonding strength is greater after cooling.
采用溶胶凝胶法在金刚石表面包覆氧化钛和氧化铝层结构，然后与荧光粉、玻璃粉颗粒、有机载体的混合均匀制成发光层，一方面由于金刚石导热率较高，使得发光层产生的热量迅速扩散出去；另一方面金刚石表面包覆的氧化钛和氧化铝层结构可以与荧光粉结合较好，且可作为白色散射粒子，可进行光的散射，或产生白光。The sol-gel method is used to coat the surface of the titanium oxide and alumina layers on the surface of the diamond, and then mixed with phosphor, glass powder particles, and organic carrier to form a light-emitting layer. On the one hand, due to the high thermal conductivity of diamond, the light-emitting layer is generated. The heat quickly diffuses out; on the other hand, the titanium oxide and aluminum oxide layer structure coated on the diamond surface can be well combined with the phosphor, and can be used as white scattering particles to scatter light or generate white light.
根据本实施例，玻璃封装无机发光层2001的质量组分可以为：YAG:Ce荧光粉占总质量的10-99％；包覆有氧化钛的金刚石占总质量的5-50％；包覆有氧化铝的金刚石占总质量的5-50％；玻璃占总质量的20-80％。较优选的方案是：YAG:Ce荧光粉占总质量的20-80％；包覆有氧化钛的金刚石占总质量的10-40％；包覆有氧化铝的金刚石占总质量的10-40％；玻璃占总质量的20-60％。According to this embodiment, the mass components of the glass-encapsulated inorganic light-emitting layer 2001 may be: YAG: Ce phosphor accounts for 10-99% of the total mass; diamond coated titanium oxide accounts for 5-50% of the total mass; Diamond with alumina accounts for 5-50% of the total mass; glass accounts for 20-80% of the total mass. The more preferred solution is: YAG: Ce phosphors account for 20-80% of the total mass; diamond-coated diamonds account for 10-40% of the total mass; alumina-coated diamonds account for 10-40 of the total mass %; Glass accounts for 20-60% of the total mass.
为了证实本发明的玻璃封装无机发光层2001相对于现有技术达到了有益效果。在实际实验中，采用了以下对比例1和对比例2的配方制备本发明的玻璃封装无机发光层2001来进行色轮测试实验以验证本发明的效果。In order to confirm that the glass-encapsulated inorganic light-emitting layer 2001 of the present invention achieves a beneficial effect compared with the prior art. In actual experiments, the following formulations of Comparative Example 1 and Comparative Example 2 were used to prepare the glass-encapsulated inorganic light-emitting layer 2001 of the present invention to perform a color wheel test experiment to verify the effect of the present invention.
在对比例1中：YAG:Ce荧光粉为总质量的30％；包覆有氧化钛的金刚石为总质量的15％；包覆有氧化铝的金刚石为总质量的15％；余下为玻璃。In Comparative Example 1: YAG: Ce phosphor is 30% of the total mass; diamond coated with titanium oxide is 15% of the total mass; diamond coated with alumina is 15% of the total mass; the rest is glass.
在对比例2中：YAG:Ce荧光粉为总质量的27％；包覆有氧化钛的金刚石为总质量的13.5％；包覆有氧化铝的金刚石为总质量的13.5％；余下为玻璃。In Comparative Example 2: YAG: Ce phosphor is 27% of the total mass; diamond-coated diamond is 13.5% of the total mass; alumina-coated diamond is 13.5% of the total mass; the rest is glass.
不含金刚石的对比例中：YAG:Ce荧光粉为总质量的27％；余下为玻璃。In the comparative example without diamond: YAG: Ce phosphor is 27% of the total mass; the rest is glass.
对不含金刚石的对比例(现有技术中的原始配方)以及本发明对比例1和对比例2中的配方进行色轮测试，测试结果的光谱图如图3所示。The color wheel test was performed on the diamond-free comparative example (the original formulation in the prior art) and the formulations in the comparative examples 1 and 2 of the present invention. The spectrum of the test results is shown in FIG. 3.
从图3的光谱图中可以看出，对比例1和对比例2的光效比原始配方好，且对比例1比原始光效提升5.4％，对比例2比原始光效提升4.6％。可见在发光层中加入金刚石后，发光层散热得到了改善，热量及时散出去，使得色轮光效升高。It can be seen from the spectrogram in FIG. 3 that the light efficiency of Comparative Example 1 and Comparative Example 2 is better than the original formula, and that of Comparative Example 1 is 5.4% higher than the original light effect, and that of Comparative Example 2 is 4.6% higher than the original light effect. It can be seen that after adding diamond to the light-emitting layer, the heat dissipation of the light-emitting layer is improved, and the heat is dissipated in time, which makes the color wheel light efficiency increase.
在本实施例中，作为金刚石原料，虽然使用了透明度低的金刚石，但是本实施例对金刚石的透明度没有严格要求，当然也可以使用无色透明的金刚石。包覆有氧化钛和氧化铝层结构的金刚石颗粒与荧光粉、玻璃粉颗粒形成发光层，包覆的氧化钛和氧化铝作用主要是加入白光散射粒子，可进行光的散射，所形成的发光层在蓝色激光下可产生白光，且金刚石导热系数为1000-2000W/(m·k)，可以与实施例1中一样，在金刚石-金刚石/金刚石-荧光粉/金刚石-荧光粉-金刚石颗粒之间可以形成空间网络结构的导热通道，将产生的热量快速扩散出去，所以这层结构既可以产生白光又可以将产生的热量迅速扩散出去。In this embodiment, although diamond with low transparency is used as the diamond raw material, the transparency of the diamond is not strictly required in this embodiment, and of course, colorless and transparent diamond can also be used. The diamond particles coated with titanium oxide and alumina layer structure form a light-emitting layer with phosphor powder and glass powder particles. The role of the coated titanium oxide and alumina is mainly to add white light scattering particles, which can scatter light and form the light. The layer can generate white light under blue laser, and the thermal conductivity of diamond is 1000-2000W / (m · k), which can be the same as in Example 1, in the diamond-diamond / diamond-fluorescent powder / diamond-fluorescent powder-diamond particles A space network structure can form a heat conduction channel between them, which can quickly diffuse the generated heat, so this layer of structure can both generate white light and quickly diffuse the generated heat.
在前述实施例中，金刚石全部被包覆，在其他实施例中也可使得部分所述金刚石表面包覆有一层氧化钛，或者部分所述金刚石表面包覆有一层氧化铝。只要有部分金刚石被二者之一包覆，即能实现优于现有技术的导热效果。In the foregoing embodiment, the diamond is entirely coated, and in other embodiments, part of the diamond surface may be covered with a layer of titanium oxide, or part of the diamond surface may be covered with a layer of alumina. As long as a part of the diamond is covered by one of the two, a thermal conductivity effect superior to the prior art can be achieved.
实施例3Example 3
在本实施例中，提供了另一种波长转换材料，即如图4所示的玻璃封装无机发光层3001，其截面示意图如图4所示。从图4可以看出，玻璃封装无机发光层3001包括荧光粉颗粒401、表面包覆有氧化钛层和氧化铝层双层结构的金刚石颗粒402和玻璃粉形成的玻璃相403。In this embodiment, another wavelength conversion material is provided, that is, the glass-encapsulated inorganic light-emitting layer 3001 shown in FIG. 4, and a schematic cross-sectional view thereof is shown in FIG. 4. As can be seen from FIG. 4, the glass-encapsulated inorganic light-emitting layer 3001 includes phosphor particles 401, diamond particles 402 with a double-layer structure of a titanium oxide layer and an aluminum oxide layer on the surface, and a glass phase 403 formed of glass powder.
本实施例中的玻璃封装无机发光层3001可以以与实施例2类似的方法来制备，其中不同之处在于，在本实施例中的所有金刚石颗粒上都包覆氧化钛层和氧化铝层双层结构。本实施例的玻璃封装无机发光层3001的制备过程如下所述。The glass-encapsulated inorganic light-emitting layer 3001 in this embodiment can be prepared by a method similar to that in Embodiment 2, except that all the diamond particles in this embodiment are covered with a titanium oxide layer and an aluminum oxide layer. Layer structure. The manufacturing process of the glass-encapsulated inorganic light-emitting layer 3001 in this embodiment is as follows.
首先，对金刚石进行清洗。金刚石粒度为2-20μm，与荧光粉颗粒粒度相匹配。将金刚石颗粒用丙酮浸泡超声清洗三次，然后干燥得到洁净的金刚石微粉。First, the diamond is washed. Diamond particle size is 2-20 μm, which matches the particle size of phosphor particles. The diamond particles were immersed in acetone for ultrasonic cleaning three times, and then dried to obtain clean diamond micropowder.
然后，将清洗干净的金刚石微粉用铜网盛装并浸泡在TiO 2溶胶中，静置1-10min，优选1min，然后以一定的速度，优选1-3cm/min，将铜网从TiO 2溶胶中提拉出来，将在TiO 2溶胶中浸泡过的金刚石放置于60-80℃的烘箱中，干燥5-10min后冷却，得到表面涂覆有TiO 2凝胶膜层的金刚石，其中膜层厚度可以为2-15μm。 Then, the cleaned diamond fine powder is contained in a copper mesh and soaked in a TiO 2 sol, and left to stand for 1-10 min, preferably 1 min, and then the copper mesh is removed from the TiO 2 sol at a certain speed, preferably 1-3 cm / min. Pull out, place the diamond soaked in TiO 2 sol in an oven at 60-80 ° C, dry it for 5-10 minutes, and cool it to obtain diamond coated with TiO 2 gel film on the surface, where the thickness of the film can be It is 2-15 μm.
接着，采用相同的实验方法在已包覆有TiO 2凝胶膜层的金刚石表面上涂覆Al 2O 3层，将表面涂覆TiO 2凝胶膜层的金刚石浸泡在Al 2O 3溶胶中，静置1-10min，优选1min，然后以一定的速度，优选1-3cm/min，将铜网从Al 2O 3溶胶中提拉出来，将涂覆有TiO 2和Al 2O 3的金刚石放置于60-80℃烘箱中，干燥5-10min后冷却，得到表面涂覆有TiO 2/Al 2O 3凝胶膜层的金刚石，其中膜层厚度2-15μm。 Next, using the same experimental method of coating the surface of Al on the diamond has been coated with a gel layer of TiO 2 2 O 3 layer, the surface-coated TiO 2 gel diamond film immersed in the Al 2 O 3 sol , Rest for 1-10min, preferably 1min, and then pull the copper mesh out of the Al 2 O 3 sol at a certain speed, preferably 1-3 cm / min, and the diamond coated with TiO 2 and Al 2 O 3 It was placed in an oven at 60-80 ° C, dried for 5-10 minutes, and then cooled to obtain diamond coated on the surface with a TiO 2 / Al 2 O 3 gel film layer, wherein the film thickness was 2-15 μm.
需要指出的是，TiO 2膜层和Al 2O 3膜层的厚度可根据涂覆的次数和提拉的速度决定，涂覆次数越多，厚度越大，提拉的速度越快，厚度越小。 It should be noted that the thickness of the TiO 2 film layer and the Al 2 O 3 film layer can be determined according to the number of coatings and the pulling speed. The more coatings, the larger the thickness, the faster the pulling speed, and the thicker the thickness. small.
接着，涂膜完成后，用马弗炉对涂膜后的金刚石进行热处理，刚开始缓慢升温至100℃，保温30min，然后以5℃/min的速度升温至600℃，保温60min，然后随炉冷却至室温，即制得表面涂覆有TiO 2/Al 2O 3双层结构的金刚石颗粒，工艺流程图如图5所示。 Next, after the coating is completed, the coated diamond is heat-treated in a muffle furnace. The temperature is slowly raised to 100 ° C for 30 minutes, and then heated to 600 ° C at a rate of 5 ° C / min for 60 minutes. After cooling to room temperature, diamond particles with a TiO 2 / Al 2 O 3 double-layer structure on the surface are prepared. The process flow chart is shown in FIG. 5.
然后，将表面包覆有氧化钛和氧化铝双层结构的金刚石与粒度为10-30um，优选为15-20um的YAG:Ce荧光粉颗粒、玻璃粉颗粒、有机载体混合均匀，然后将混合均匀的浆料直接印刷在氮化铝陶瓷基板上，印刷的浆料的厚度为约50-120um，最后将其上印刷有浆料的上述氮化铝陶瓷基板放入马弗炉中进行烧结，烧结温度为700-1000℃，保温30min-1h，从而获得上述玻璃封装无机发光层3001。需要指出的是，YAG:Ce荧光粉颗粒占整个玻璃封装无机发光层3001的质量百分比范围为10％-99％，优选为30％-80％以达到良好的发光效果；表面包覆有氧化钛和氧化铝的金刚石与荧光粉的比例为1:(1-5)，优选1:1。Then, the diamond coated with the titanium oxide and alumina double-layer structure on the surface and the YAG: Ce phosphor particles, glass powder particles, and organic carrier having a particle size of 10-30um, preferably 15-20um are mixed uniformly, and then the mixture is uniformly mixed. The paste is printed directly on the aluminum nitride ceramic substrate. The thickness of the printed paste is about 50-120um. Finally, the above aluminum nitride ceramic substrate printed with the paste is placed in a muffle furnace for sintering and sintering. The temperature is 700-1000 ° C, and the temperature is maintained for 30 min-1 h, so as to obtain the glass-encapsulated inorganic light-emitting layer 3001. It should be noted that the mass percentage of YAG: Ce phosphor particles in the entire glass-encapsulated inorganic light-emitting layer 3001 ranges from 10% to 99%, preferably 30% to 80% to achieve a good light emitting effect; the surface is coated with titanium oxide The ratio of diamond to phosphor of alumina is 1: (1-5), preferably 1: 1.
在本实施例中与实施例2中一样，氧化钛溶胶和金刚石的润湿性较好，氧化钛溶胶是以非极性有机类物质为环境，而金刚石是正四面体结 构，其表面极性键较少，容易被非极性类水溶液润湿，所以氧化钛溶胶在金刚石表面的润湿性较好，即易被氧化钛溶胶包裹。氧化铝溶胶在被氧化钛溶胶包覆的金刚石表面上能够很好的铺展。由于金刚石形状不规则，很多有棱角，金刚石颗粒棱角处也被膜层包覆的较好。被包覆后的金刚石抗氧化性能得到大幅度提高。烧结过程中的玻璃相和被包覆的金刚石能够很好的润湿，冷却后结合强度较大。In this example, as in Example 2, titanium oxide sol and diamond have better wettability. The titanium oxide sol uses a non-polar organic substance as the environment, while diamond has a regular tetrahedron structure, and its surface has polar bonds. Less, easy to be wetted by non-polar aqueous solution, so the titanium oxide sol has better wettability on the diamond surface, that is, it is easy to be wrapped by the titanium oxide sol. Alumina sol can spread well on the surface of diamond coated with titanium oxide sol. Due to the irregular shape of the diamond, many have edges and corners, and the diamond particles are better covered by the film. The oxidation resistance of the coated diamond has been greatly improved. During the sintering process, the glass phase and the coated diamond can be well wetted, and the bonding strength is greater after cooling.
采用溶胶凝胶法在金刚石表面包覆氧化钛层和氧化铝层双层结构，然后与荧光粉、玻璃粉颗粒、有机载体的混合均匀制成发光层，一方面由于金刚石导热率较高，使得发光层产生的热量迅速扩散出去；另一方面金刚石表面包覆的氧化钛和氧化铝层结构可以与荧光粉结合较好，且可作为白色散射粒子，可进行光的散射，或产生白光。The sol-gel method is used to coat the double-layered structure of titanium oxide layer and aluminum oxide layer on the diamond surface, and then mixed with phosphor powder, glass powder particles, and organic carrier to form a light-emitting layer. The heat generated by the light-emitting layer is quickly diffused out; on the other hand, the titanium oxide and aluminum oxide layer structure coated on the surface of the diamond can be well combined with the phosphor, and can be used as white scattering particles to scatter light or generate white light.
同样，在本实施例中，对金刚石透明度没有严格要求，包覆有氧化钛层和氧化铝层双层结构的金刚石颗粒与荧光粉、玻璃粉颗粒形成发光层，包覆的氧化钛和氧化铝作用主要是加入白光散射粒子，可进行光的散射，所形成的发光层在蓝色激光下可产生白光，且金刚石导热系数为1000-2000W/(m·k)，可以与实施例1和实施例2中一样，在金刚石-金刚石/金刚石-荧光粉/金刚石-荧光粉-金刚石颗粒之间可以形成空间网络结构的导热通道，将产生的热量快速扩散出去，所以这层结构既可以产生白光又可以将产生的热量迅速扩散出去。本实施例的光效和实施例2中光效相差不大，比原始光效均有提升。Similarly, in this embodiment, there is no strict requirement for diamond transparency. Diamond particles coated with a two-layer structure of titanium oxide layer and aluminum oxide layer form a light-emitting layer with phosphor powder and glass powder particles, and the coated titanium oxide and aluminum oxide The function is mainly to add white light scattering particles, which can scatter light. The formed luminescent layer can generate white light under blue laser light, and the thermal conductivity of diamond is 1000-2000W / (m · k), which can be used with Example 1 and implementation. As in Example 2, a thermal conduction channel with a spatial network structure can be formed between diamond-diamond / diamond-phosphor / diamond-phosphor-diamond particles, and the generated heat can be quickly diffused out, so this layer of structure can produce both white light and The heat generated can be quickly dissipated. The light effect in this embodiment is not much different from the light effect in Embodiment 2, and is improved over the original light effect.
本发明所列举的各原料，以及本发明各原料的上下限、工艺参数的上下限、区间取值都能实现本发明，在此不一一列举实施例；凡是依据本发明的技术实质对以上实施例所作的任何简单修改或等同变化，均仍属于本发明的技术方案的范围之内。Each of the raw materials listed in the present invention, as well as the upper and lower limits of each raw material of the present invention, the upper and lower limits of the process parameters, and the value of the interval can achieve the present invention, and the examples are not listed here one by one; Any simple modification or equivalent change made by the embodiments still falls within the scope of the technical solution of the present invention.

Claims (11)

  1. 一种波长转换材料，其特征在于，所述波长转换材料包含金刚石、荧光粉和玻璃相，所述荧光粉占所述波长转换材料总质量的10％-99％，所述金刚石与所述荧光粉的比例为1:(1-5)，优选1:1。A wavelength conversion material, characterized in that the wavelength conversion material includes diamond, phosphor and glass phase, the phosphor powder accounts for 10% -99% of the total mass of the wavelength conversion material, and the diamond and the fluorescence The ratio of powder is 1: (1-5), preferably 1: 1.
  2. 根据权利要求1所述的波长转换材料，其特征在于，至少部分所述金刚石与相邻的金刚石或者荧光粉之间接触从而形成空间网络结构的导热通道。The wavelength conversion material according to claim 1, wherein at least a part of the diamond is in contact with an adjacent diamond or phosphor to form a thermally conductive channel in a space network structure.
  3. 根据权利要求2所述的波长转换材料，其特征在于，至少部分所述金刚石表面包覆有一层氧化钛，或者至少部分所述金刚石表面包覆有一层氧化铝。The wavelength conversion material according to claim 2, wherein at least part of the surface of the diamond is coated with a layer of titanium oxide, or at least part of the surface of the diamond is coated with a layer of alumina.
  4. 根据权利要求2所述的波长转换材料，其特征在于，一部分所述金刚石表面包覆有一层氧化钛，同时另一部分所述金刚石表面包覆有一层氧化铝。The wavelength conversion material according to claim 2, wherein a part of the surface of the diamond is coated with a layer of titanium oxide, and a part of the surface of the diamond is coated with a layer of alumina.
  5. 根据权利要求4所述的波长转换材料，其特征在于，所述氧化钛包覆层的厚度和所述氧化铝包覆层的厚度均为2-15μm。The wavelength conversion material according to claim 4, wherein the thickness of the titanium oxide coating layer and the thickness of the aluminum oxide coating layer are both 2-15 μm.
  6. 根据权利要求4所述的波长转换材料，其特征在于，包覆有氧化钛的所述金刚石与包覆有氧化铝的所述金刚石的质量比为1:(1-10)。The wavelength conversion material according to claim 4, wherein a mass ratio of the diamond coated with titanium oxide to the diamond coated with aluminum oxide is 1: (1-10).
  7. 根据权利要求4所述的波长转换材料，其特征在于，The wavelength conversion material according to claim 4, wherein:
    所述荧光粉占所述波长转换材料总质量的10％-99％，优选为20-80％；The phosphor accounts for 10% -99%, preferably 20-80% of the total mass of the wavelength conversion material;
    包覆有氧化钛的所述金刚石占所述波长转换材料总质量的5-50％，优选为10-40％；The diamond coated titanium oxide accounts for 5-50%, preferably 10-40% of the total mass of the wavelength conversion material;
    包覆有氧化铝的所述金刚石占所述波长转换材料总质量的5-50％，优选为10-40％；The diamond coated with alumina accounts for 5-50%, preferably 10-40% of the total mass of the wavelength conversion material;
    所述玻璃相占所述波长转换材料总质量的20-80％，优选为20-60％。The glass phase accounts for 20-80%, preferably 20-60% of the total mass of the wavelength conversion material.
  8. 根据权利要求2所述的波长转换材料，其特征在于，The wavelength conversion material according to claim 2, wherein:
    所述金刚石的表面包覆有一层氧化钛，并且在氧化钛的表面还包覆有一层氧化铝。The surface of the diamond is coated with a layer of titanium oxide, and the surface of the titanium oxide is further coated with a layer of alumina.
  9. 根据权利要求8所述的波长转换材料，其特征在于，The wavelength conversion material according to claim 8, wherein:
    所述氧化钛和氧化铝的包覆层的厚度为2-15μm。The thickness of the coating layer of titanium oxide and aluminum oxide is 2-15 μm.
  10. 一种波长转换材料的制备方法，所述方法包括以下步骤：A method for preparing a wavelength conversion material. The method includes the following steps:
    S1：准备粒度为2-20μm的金刚石颗粒以及粒度为10-30um、优选为15-20um的荧光粉颗粒、能够在600-800℃烧结的玻璃粉颗粒；S1: prepare diamond particles with a particle size of 2-20 μm, phosphor particles with a particle size of 10-30 um, preferably 15-20 um, and glass powder particles that can be sintered at 600-800 ° C;
    S2：采用溶胶凝胶法在一部分所述金刚石颗粒的表面包覆一层氧化钛，并在另一部分所述金刚石颗粒的表面包覆一层氧化铝；S2: using a sol-gel method to coat a portion of the surface of the diamond particles with a layer of titanium oxide, and coating a surface of the diamond particles with a layer of alumina;
    S3：将步骤S2中制备得到的表面具有包覆层的所述金刚石颗粒、所述荧光粉颗粒、所述玻璃粉颗粒以及有机载体混合均匀以制成浆料，并将该浆料印刷在陶瓷基板上；和S3: The diamond particles, the phosphor particles, the glass powder particles, and the organic carrier having the coating layer on the surface prepared in step S2 are mixed uniformly to make a paste, and the paste is printed on a ceramic On the substrate; and
    S4：将步骤S3中制备得到的其上印刷有浆料的陶瓷基板进行烧结，制得所述波长转换材料。S4: Sintering the ceramic substrate having the paste printed thereon prepared in step S3 to obtain the wavelength conversion material.
  11. 一种波长转换材料的制备方法，所述方法包括以下步骤：A method for preparing a wavelength conversion material. The method includes the following steps:
    S1：准备粒度为2-20μm的金刚石颗粒、粒度为10-30um，优选为15-20um的荧光粉颗粒、能够在600-800℃烧结的玻璃粉颗粒；S1: prepare diamond particles with a particle size of 2-20 μm, phosphor particles with a particle size of 10-30 um, preferably 15-20 um, and glass powder particles that can be sintered at 600-800 ° C;
    S2：采用溶胶凝胶法在所有金刚石颗粒的表面包覆一层氧化钛，然后在包覆有氧化钛的金刚石颗粒的表面上再包覆一层氧化铝；S2: The surface of all diamond particles is coated with a layer of titanium oxide by a sol-gel method, and then a layer of aluminum oxide is coated on the surface of the diamond particles coated with titanium oxide;
    S3：将步骤S2中制备得到的表面具有一层氧化钛和一层氧化铝的双包覆层的所述金刚石颗粒、所述荧光粉颗粒、所述玻璃粉颗粒以及有机载体混合均匀以制成浆料，并将该浆料印刷在陶瓷基板上；和S3: The diamond particles, the phosphor particles, the glass powder particles, and the organic carrier are prepared by mixing the diamond particles, the phosphor particles, the glass powder particles, and the organic carrier on the surface prepared in step S2 with a double coating of titanium oxide and alumina. Paste, and printing the paste on a ceramic substrate; and
    S4：将步骤S3中制备得到的其上印刷有浆料的陶瓷基板进行烧结，制得所述波长转换材料。S4: Sintering the ceramic substrate having the paste printed thereon prepared in step S3 to obtain the wavelength conversion material.
PCT/CN2019/100491 2018-09-25 2019-08-14 Wavelength conversion material of high thermal conductivity WO2020063160A1 (en)

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